Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt

ABSTRACT

WATER-DISSIPATABLE, MELTABLE POLYESTERS AND POLYESTERAMIDES DERIVED FROM MONOMER COMPONENTS WHICH INCLUDE DICARBOXYLIC ACID, HYDROXYCARBOXYLIC ACID, AMINOCARBOXYLIC ACID, AMINOALCOHOL, GLYCOL, DIAMINE OR COMBINATIONS OF SUCH MONOMER COMPONENTS WHEREIN AT LEAST A PART OF THE TOTAL OF ALL SUCH MONOMER COMPONENTS IS A POLY (ETHYLENE GLYCOL), AND AT LEAST A PART OF SAID TOTAL IS ONE OR MORE OF SAID MONOMER COMPONENTS SUBSTITUTED WITH ONE OR MORE SULFONATE METAL SALT GROUPS. A TYPICAL POLYESTER IS COMPOSED OF 80 MOLE PARTS OF ISOPHTHALIC ACID, 10 MOLE PARTS OF ADIPIC ACID, 10 MOLE PARTS OF 5-SODIOSULFOISOPHTHALATE, 20 MOLE PARTS OF ETHYLENE GLYCOL AND 80 MOLE PARTS DIETHYLENE GLYCOL. SUCH POLYMERS ARE USEFUL AS ADHESIVES, COATING MATERIALS, FILMS, PACKAGING MATERIALS AND OTHER PRODUCTS WHICH CAN BE DISSOLVED, DISPERSED OR OTHERWISE DISSIPATED IN COLD WATER, HOT WATER OR AQUEOUS SOLUTIONS.

United States Patent 3,734,874 POLYESTERS AND POLYESTERAMIDES CONTAIN-ING ETHER GROUPS AND SULFONATE GROUPS IN THE FORM OF A METALLIC SALTCharles J. Kibler and Gerald R. Lappin, Kingsport, Tenm, assignors toEastman Kodak Company, Rochester, N.Y. No Drawing. Continuation-impartof application-Ser. No. 695,339, Jan. 3, 1968. This application Feb. 27,1970, Ser. No. 15,193

Int. Cl. C08g 17/06, 20/30 US. Cl. 260-292 E 40 Claims ABSTRACT OF THEDISCLOSURE Water-dissipatable, meltable polyesters and polyesteramidesderived from monomer components which include dicarboxylic acid,hydroxycarboxylic acid, aminocarboxylic acid, aminoalcohol, glycol,diamine or combinations of such monomer components wherein at least apart of the total of all such monomer components is a poly(ethyleneglycol), and at least a part of said total is one or more of saidmonomer components substituted with one or more sulfonate metal saltgroups. A typical polyester is composed of 80 mole parts of isophthalicacid, 10 mole parts of adipic acid, 10 mole parts ofS-sodiosulfois'ophthalate, 20 mole parts of ethylene glycol and 80 moleparts diethylene glycol. Such polymers are useful as adhesives, coatingmaterials, films, packaging materials and other products which can bedissolved, dispersed or otherwise dissipated in cold water, hot water oraqueous solutions.

This application is a continuation-in-part of our application Ser. No.695,339, filed Jan. 3, 1968, now abandoned.

The present invention relates to the preparation and some uses of novellinear, water-dissipatable polymers which are meltable and have goodadhesive properties. More particularly, this invention relates towater-dissipatable polyesters and polyesteramides which in oneembodiment are prepared by reacting a glycol component, a dicarboxylicacid component, and at least one difunctional comonomer wherein aportion of said comonomer contains a sulfonate group in the form of ametallic salt, said sulfonate group being attached to an aromaticnucleus. Other embodiments are disclosed hereinafter.

The incorporation of extremely low concentrations of alkali metal saltsof sulfoisophthalic acid or other sulfoacids into a fiber-formingpolyester or the like for the purpose of improving the dyeability of thefiber has been taught in a number of patents. None of these references,however, are concerned with a water-dissipatable polyester orpolyesteramides, nor do they teach (1) the preparation of a polymer froma glycol of which at least 15 mole percent is a poly(ethylene glycol),i.e., a poly- (oxyethylene glycol), or (2) such a preparation Where thetotal of all components contains at least about 8 mole percent of apoly(ethylene glycol). One of these patents, US. 3,018,272, disclosesthe use of a variety of sulfoacids, including -sulfoisophthalic acid.The upper limit of sulfoacid concentration disclosed in this patent,however, is 10 mole percent of the total acid components and thepolymers identified therein are not water-dissipatable and do notcontain poly(oxyalkylene) glycols. A Japanese patent application No.12,149/62 (apparently published on Aug. 27, 1962) discloses in atranslated English abstract that polyester copolymers are prepared fromterephthalic acid, sodium sulfophthalic acid or other sulfo-carboxylicacids, glycols having 2-1O carbon atoms and poly(oxyalkylene glycols);however the sulfo-carboxylic acid component is said to be used in anamount of l-5 mole percent based on terephthalic acid residues in thecopolymer produced, and the illustrated polyoxyethylene glycol has amolecular weight of 4,000 and is used in an amount of 2 parts along with70 parts of ethylene glycol (mol. Wt. of 62); hence, 2 parts representsa very small fraction of one mole percent based on the total glycolsused. The resulting polymers clearly lack the characteristics of beingwater-dissipatable.

According to the present invention, both polyesters and polyesteramidesas defined herein have the same characteristic of beingwater-dissipatable; hence, it is considered most appropriate to coverall these polymers in one specification; however, certain polyesters assubgeneric subject matter are especially advantageous.

In accordance with one aspect of the present invention, a linear,water-dissipatable, meltable polyester or polyesteramide, having aninherent viscosity of at least 0.1 and advantageously (in some cases) atleast 0.3, is prepared from a glycol component, a dicarboxylic acidcomponent, and a difunctional monomer component. The components used inthe polymer condensation products of this invention are all essentiallydifunctional which means that they cannot contain other substituentssuch as isocyanate groups since any such third functional group wouldmean that the compound was trifunctional. The two functional groupswhich are present condense to form carbonyl'oxy or carbonylamidointerconnecting groups in the linear molecular structure. The glycolcomponent of the invention advantageously comprises at least about 15mole percent of at least one poly(ethylene glyc'ol( having the formula:

HOOH2CH2 n wherein n is 2 to about 20.

More especially, this invention provides a linear, water-dissipatablepolymer having carbonyloxy interconnecting groups in the linearmolecular structure wherein up to thereof may be carbonylamido linkinggroups, said polymer having an inherent viscosity of at least about 0.1measured in a 60/40 parts by weight solution of phenol/tetrachloroethaneat 25 C. and at a concentration of about 0.25 gram of polymer in ml. ofsaid solvent, said polymer consisting essentially of at least (a), (b)and (c) from the following components:

(a) At least one difunctional dicarboxylic acid;

(b) At least one difunctional glycol containing two CR OH groups ofwhich at least 15 mole percent is a poly (ethylene glycol) having thestructural formula:

n being an integer in the range between about 2 and about 20;

(0) An amount sufiicient to provide said water-dissipata'blecharacteristic of said polymer of at least one difunctionalsulfo-monomer containing at least one metal sulfonate group attached toan aromatic nucleus wherein the functional groups are hydroxy, carboxylor amino; and

(d) From none to an amount of a difunctional hydroxycarboxylic acidhaving one CR -OH group, an aminocarboxylic acid having one NRH group,an. amino--alcohol having one CR -OH group and one NRH group, a diaminehaving two NRH groups, or a mixture thereof, wherein each R is an H atomor a 1-4 carbon alkyl group, said components (a), (b), (c) and (d) beingorganic compounds, each of which contains a hydrocarbon moiety which hasfrom none up to six nonfunctional groups, and where (A) represents allof the carboxy functional groups in said polymer from all of saidcomponents and (B) represents all of the functional hydroxy andfunctional amino groups in said polymer from all of said components, theratio of said (A) to (B) in said polymer is substantially unity, wherebysaid polymer is essentially linear. Acording to one aspect of thisinvention, there is provided a polymer which is a polyester wherein saiddifunctional sulfo-monomer is a dicarboxylic acid and constitutes about8 mole percent to about 50 mole percent based on the sum of (1) themoles of the total dicarboxylic acid content of components (a) and (b),and (2) one half of the moles of any hydroxycarboxylic acid content fromsaid component (d).

According to more specific embodiments, such polyesters are providedwherein said difunctional sulfo-monomer (c) is a glycol and constitutesabout 8 mole percent to about 50 mole percent based on the sum of (1)the total glycol content measured in moles of (b) and (c), and (2) onehalf of the moles of any hydroxycarboxylic acid content from saidcomponent (d).

The aforesaid range is most preferably from about 10 up to about 50 molepercent.

Examples of suitable poly(ethylene glycols) include diethylene glycol,triethylene glycol, tetraethylene glycol, and pentaethylene,hexaethylene, heptaethylene, octaethylene, nonaethylene, anddecaethylene glycols, and mixtures thereof. Preferably the poly(ethyleneglycol) employed in the polyesters or polyesteramides of the presentinvention is diethylene glycol or triethylene glycol or mixturesthereof. The remaining portion of the glycol component may consist ofaliphatic, alicyclic, and aralkyl glycols. Examples of these glycolsinclude ethylene glycol; propylene glycol; 1,3-propanediol;2,4-dimethyl-2-ethylhexane-1,3-diol; 2,2-dimethyl-1,3-propanediol;2-ethyl-2- butyl-1,3-propanediol; 2-ethyl-2-isobutyl-1,3-propanediol;1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol;2,2,4-trimethyl-1,6-hexanediol; thiodiethanol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-1,3-cyclobutanediol;p-xylylenediol. Copolymers may be prepared from two or more of the aboveglycols.

The dicarboxylic acid component of the polyester or polyesteramidecomprises aliphatic dicarboxylic acids, alicyclic dicarboxylic acids,aromatic dicarboxylic acids, or mixtures of two or more of these acids.Examples of such dicarboxylic acids include oxalic; malonic;dimethylmalonic; succinic; glutaric; adipic; trirnethyladipic; pimelic;2,2-dimethylglutaric; azelaic; sebacic; fumaric; maleic; itaconic;1,3-cyclpentanedicarboxylic; 1,2-cyclohexanedicarboxylic;1,3-cyclohexanedicarboxylic; 1,4cyclohexanedicarboxylic; phthalic;terephthalic; isophthalic; 2,5-norbornanedicarboxylic; 1,4-naphthalic;diphenic; 4,4- oxydibenzoic; diglycolic; thiodipropionic; 4,4-sulfonyldibenzoic; and 2,S-naphthalenedicarboxylic acids. If terephthalic acid isused as the dicarboxylic acid component of the polyester, superiorresults are achieved when at least mole percent of one of the otheracids listed above is also used.

It should be understood that use of the corresponding acid anhydrides,esters, and acid chlorides of these acids is included in the termdicarboxylic acid. Examples of these esters include dimethyl1,4-cyclohexanedicarboxylate; dimethyl 2,6-naphthalenedicarboxylate;dibutyl 4,4- sulfonyldibenzoate; dimethyl isophthalate; dimethylterephthalate; and diphenyl terephthalate. Copolyesters may be preparedfrom two or more of the above dicarboxylic acids or derivatives thereof.

The difunctional sulfo-monomer component of the polyester orpolyesteramide may advantageously be a dicarboxylic acid or an esterthereof containing a metal sulfonate group or a glycol containing ametal sulfonate group or a hydroxy acid containing metal sulfonategroup. The metal ion of the sulfonate salt may be Na Li K Mg++, Ca++, CuNi++, Fe++, Fe+++ and the like. When a monovalent alkali metal ion isused the resulting polyesters or polyesteramides are less readilydissipated by cold water and more readily dissipated by hot water. Whena divalent or a trivalent metal ion is used the resulting polyesters orpolyesteramides are not ordinarily easily dissipated by cold water butare more readily dissipated in hot water. Depending on the end use ofthe polymer, either of the different sets of properties may bedesirable. It is possible to prepare the polyester or polyesteramideusing, for example, a sodium sulfonate salt and later by ion-exchangereplace this ion with a different ion, for example, calcium, and thusalter the characteristics of the polymer. In general, this procedure issuperior to preparing the polymer with divalent metal salt inasmuch asthe sodium salts are usually more soluble in the polymer manufacturingcomponents than are the divalent metal salts. Polymers containingdivalent or trivalent metal ions are less elastic and rubber-like thanpolymers containing monovalent ions. The difunctional monomer componentmay also be referred to as a difunctional sulfo-monomer and is furtherdescribed hereinbelow.

Advantageous difunctional components which are aminoalcohols includearomatic, aliphatic, heterocyclic and other types as in regard tocomponent ((1). Specific examples include S-aminopentanol-l,4-aminomethylcyclohexanemethanol, 5-amino-2-ethyl-pentanol-l, 2-(4-B-hydroxyethoxyphenyl)-1-aminoethane, 3-amino-2,2-dimethylpropanol,hydroxyethylamine, etc. Generally these aminoalcohols contain from 2 to20 carbon atoms, one -NRH group and one CR -OH group.

Advantageous difunctional monomer components which are aminocarboxylicacids include aromatic aliphatic, heterocyclic, and other types as inregard to component (d) and include lactams. Specific examples include6-aminocaproic acid, its lactam known as caprolactam,omega-aminoundecanoic acid, S-amino-Z-dimethylpropionic acid,4-(B-aminoethyl)benzoic acid, 2-(B- aminopropoxy)benzoic acid,4-aminomethylcyclohexanecarboxylic acid, 2 (5aminopropoxy)cyclohexanecarboxylic acid, etc. Generally these compoundscontain from 2 to 20 carbon atoms.

Advantageous examples of difunctional monomer component (d) which arediamines include ethylenediamine; hexamethylenediamine;2,2,4-trimethylhexamethylenediamine; 4-oxaheptane-1,7-diamine;4,7-dioxadecane-1,10- diamine; 1,4 cyclohexanebismethylamine; 1,3cycloheptamethylenediamine; dodecamethylenediamine, etc.

Advantageous difunctional sulfo-monomer components are those wherein thesulfonate salt group is attached to an aromatic acid nucleus such as abenzene, naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl, ormethylenediphenyl nucleus. Preferred results are obtained through theuse of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalicacid, 4 sulfonaphthalene-2,7 dicarboxylic acid, and their esters;metallosulfoaryl sulfonate (as described in Lappin, Kibler, Gilmer, andJones US. patent application Ser. No. 695,349, entitled New OrganicCompounds and Basic-Dyeable Polyesters Containing Same, filed Jan. 3,1968) having the general formula:

wherein X is a trivalent aromatic radical derived from a substituted orunsubstituted aromatic hydrocarbon, Y is a divalent aromatic radicalderived from a substituted or unsubstituted aromatic hydrocarbon, A andB are carboalkoxy groups containing 1 to 4 carbon atoms in the alkylportion or a carboxy group, M is Li+, Na K Mg++, Ca++, Cu++, Fe++,Fe+++, and n is 1 for monovalent M or 2 for divalent M. The precedingsulfomonomer compounds may be prepared as shown by the following generalreactions which are exemplified in the examples below:

(1) R000 R000 P615 g X-SOaM x -01 ll R000 R000 g I Base x- -01+HO-Y-SO3M X- OYSOaM ROOO Many variations of these reactions may beemployed. For example, the sulfonyl chloride intermediate may beprepared from either the sulfonic acid or a salt thereof, and otherchlorinating agents (e.g., thionyl chloride, phosphorus trichloride,phosphorous oxychloride) may be used. In addition, the reaction betweenthe sulfonyl chloride and the sulfophenol may be carried out in water oran inert organic solvent, and the base used may be an alkali metalhydroxide or a tertiary amine.

Examples of preferred modifiers include:

(A) 4-sodiosnlfopheny1-3,5-diearbomethoxybenzenesulfonate CHaOOO (B)4-Llthlosulfopheny1-3,5-dicarbomethoxybenzenesulfonate (C)4-s0d1osulf0-2,6-dimethy1phenyl-3,5-d1carbomethoxybenzenesulfonateCHsOOC CH3 Q-sw-o-Qsonm 0113000 Ha (D)4-s0di0sulfo-2,6-dipropylphenyl-3,5-dloarbomethoxybenzenesulfonate CHaOOC CsH7 Qsm-oQsmm CHaOO (E)4-sod10sulfo1-naphthyl-3,5-d1carbomethoxybenzenesulfonate CHaOOC SO2Osome (E) fi'sodlosulfo-1-napl1thy1-3,5-dlcarbomethoxybenzenesulfonateCHaOOC 013300 0 SOsNa (G)sodiosulfo-l-naphthyl-3,5-d1carbomethoxybenzenesulfonate CHaOOO OaNa (H)4-sodiosulfophenyl-3,B-dicarbethoxybenzenesulfonate (EH 0 O 0 (I)sodiosulfophenyL3,5-dicarbopr0poxybenzenesulfonate O3H O O O (J)sodiosulfophenyl-3,5-dicarbobutoxybenzenesulfonate C4H9O O C C 4H9 O O C(K) 3-sodi0sulfophenyl-3,5dlcarbomethoxybenzenesulfonate CH3 0 0 C S OaNa (L) 4-s0diosulfophenyl-3,E-dicarboxybenzenesulfonate sm-oQsmm (M)4-sodlosulfophenyl-3,4-dicarbomethoxybenzenesulfonate CHaOOC (N)4-sodiosulfopheny1-2,5-dicarbomethoxybenzenesulfonate (0)2-sodlosu1fopheny1-3,5-diearbomethoxybenzenesulfonate OH OOC S OaNaCHaOOO CHsOOJJ (1?)4-potassi0sulfopheny1-3,fi-dicarbomethoxyhenzenesulfonate (R)8-sodiosu1fo-1-naphthyl-3,S-dlcarbomethoxybenzenesulfona CHsOOC 011.000NBIOBSQ (S) 6-sodiosulfo-2-naphthyl-3,5-dlcarbomethoxybenzenesulfonateCHaOOC In the new organic compounds of said invention, the two functiongroups on the trivalent radical X may be in any positional relationshipto each other and to the metallic sulfonate group.

Other advantageous sulfo-monomer components include alkali metal saltsof a sulfodiphenyl ether dicarboxylic acid or its ester as described inLappin et al., U.S. patent application Ser. No. 671,565, filed Sept. 29,1967, now abandoned and substituted by streamlined continuation Ser. No.835,295, which was published Nov. 18, 1969 as a Defensive Publication,868 O.G. 730. These compounds have the general formula:

ROOC SOsM no-orpom-oQo o-oom Another illustrative example of component(c) has the following formula:

soaNa When the sulfonate-containing difunctional monomer is an acid orits ester, the polyester or polyesteramide should contain at least 8mole percent of said monomer based on total acid content, with more than10 mole percent giving particularly advantageous results. Total acidcontent is calculated as the sum of 1) moles of component (a) namely,dicarboxylic acids, (2) one half of the moles of carboxyl-containingcompounds of component (d), (3) moles of component (0) which aredicarboxylic acids, and (4) one half of the moles of component (c) whichare monocarboxy-containing compounds.

When the difunctional sulfo-monomer is a glycol containing a metalsulfonate group, the polyester or polyesteramide should contain at least8 mole percent of the sulfo-monomer based on total hydroxy content andany amino content from a monomer component, with more than 10 molepercent giving particularly advantageous results. Total hydroxy andamino content from monomer components obviously excludes the oxy atomsinternally present in the poly(ethylene glycol) and is calculated as thesum of (1) moles of component (b), (2) one half of the moles of anycarboxyl-containing compounds of component (d), (3) any moles ofcomponent (d) which are amino-alcohols and diamines, (4) one half of themoles of component (c) which are mono-hydroxy or mono-amino containingcompounds, and (5) moles of component (c) which are dihydroxy, diaminoand arninohydroxy compounds.

Greater dissipatability is achieved when the difunctional sulfo-monomerconstitutes from about 6 mole percent to about 25 mole percent out of atotal of 200 mole percent of (a), (b), (c) and any (d) components of thepolyester or polyesteramide. The total of 200 mole percent is explainedbelow and can also be referred to as 200 mole parts.

Any of the above-identified difunctional monomers generally containhydrocarbon moieties having from 1 to about 40 carbon atoms in additionto their two functional groups, but they may in general also contain upto six non-functional groups such as -O, S-, -SO SO O, etc. Of course,the poly(ethylene glycol) monomer used may contain from 1 to about 19oxy groups, namely O groups.

By changing the proportions of the various acids which make up thedicarboxylic acid component of the polyester or polyesteramide, theproperties of the polymer may be varied to meet specific end uses.Therefore, as the proportion of terephthalic acid is decreased, thepolymer becomes more flexible. Thus, wide ranges of softening point andflexibility can be obtained by varying the proportions of the variousacids employed as the dicarboxylic acid component. Moreover, varying themole percentages of sulfonate-containing difunctional monomer varies thewater susceptibility of the polymer. In addition, the mixture ofdissipated polymer and aqueous solution is unexpectedly stable, thusdemonstrating the hydrolytic stability of the polymer. Furthermore,essentially no hydrolysis of the polymer occurs during three monthsstorage at room temperature in water and even at 50 C. in water thepolymer resists hydrolytic degradation for several days.

To obtain the modified polymers of this invention, thesulfonate-containing difunctional monomer modifier may be added directlyto the reaction mixture from which the polymer is made, Thus, thesemonomer modifiers can be used as a component in the original polymerreaction mixture. Other various processes which may be employed inpreparing the novel polymers of this invention are well known in the artand are illustrated in such patents as U.S. 2,465,319; 3,018,272;2,901,466; 3,075,952; 3,033,- 822; 3,033,826 and 3,033,827. Thesepatents illustrate interchange reactions as well as polymerization orbuild-up processes.

Whenever the term inherent viscosity (\LV.) is used in this description,it will be understood to refer to viscosity determinations made at 25 C.using 0.25 gram of polymer per ml. of a solvent composed of 60 percentphenol and 40 percent tetrachloroethane as parts by weight. In addition,whenever the terms dissipatable, dissipated or dissipate, are used inthis description, it

will be understood to refer to the activity of a water, aqueous orcaustic aqueous solution on the polymer. The terms are specificallyintended to cover those situations wherein the solution dissolves and/ordisperses the polyester or polyesteramide therein and/or therethrough.Furthermore, whenever the word water is used in this de scription, itincludes not only aqueous solutions but also hot aqueous solutions andcaustic aqueous solutions.

The polyesters and polyesteramides of this application have particularutility in the paper-using industry as a hot-melt adhesive which willdissipate in aqueous or caustic aqueous solutions. In many operationsusing paper products, it is advantageous to use a hot-melt adhesive forvarious sealing or fastening operations as, for example, in making paperbags or in book binding. Such operations produce a significant amount ofscrap paper which can be recovered by repulping and adding this pulpback in the paper-making prooess. Conventional hot-melt adhesive are notaffected by the hot alkaline solutions used in repulping and seriouslyinterfere with successful recovery of paper scrap.

The present invention, however, provides hot-melt adhesives which aredissolved or dispersed by hot aqueous solutions, and, therefore, do notinterfere with the repulping process. Many other uses exist for such aWater dissipatable hot-melt adhesive. In addition, the presentpolyesters and polyesteramides have utility as hot-melt adhesives forpaper, cloth, polyester film and other substrates. Because of theirwater dissipatability, the polymers of this invention have many uses notopen to ordinary hot-melt adhesives. For example, it is possible toapply a water solution of the polymer to a substrate, allow the water toevaporate leaving an adherent coating of the polymer on the substrate.At some later time a bond can be formed by application of heat andpressure. Another application of this invention involves water-solublefilms which are used for packaging detergents, dry bleach, and suchproducts. With the use of the present polyester or polyesteramide, it ispossible to put package and all in a washing machine whereupon thepackage disintegrates readily in hot water but is relatively unaffectedby moisture at ordinary temperatures. Films of the present watersolublepolymer, particularly those in which the metal ion is Mg++ or Ca++, havesuch properties and are useful for this application. There are manyapplications for a surface coating material which can be easily appliedto give a tough adherent protective coating which can later be easilyremoved. These new polymers have properties which make them useful forthis purpose. Other uses for the polymers of this invention include usesfor film splicmg.

Additional uses are disclosed in Shields, Hawkins and Wooten US. Pat.3,456,008 entitled Sizing Compositions 10 This invention will be furtherillustrated by the following examples. The percentages are by weightunless otherwise specified.

EXAMPLE 1 A mixture of (a-l) 48.5 g. (0.25 mole) of dimethylisophthalate, (a-Z) 24.2 g. (0.125 mole) of dimethyl terephthalate,(a-3) 15 g. (0.075 mole) of hexahydroisophthalic acid, (c) 14.8 g. (0.05mole) of dimethyl 5- sodiosulfoisophthalate, (b) 68.9 g. (0.65 mole) ofdiethylene glycol, 0.8 ml. of a 21% catalyst solution of titaniumisopropoxide and 0.41 g. (0.005 mole) of sodium acetate as a buffer.This mixture is stirred and heated at 200 C. for 2 hours. Note thatcomponents (a-l), (a-Z) and (c) are dicarboxylic acid components (totalof 0.500 mole or 100 mole percent based on such acid components), andnote further that the glycol component (b) in excess of 0.5 mole isreduced to an amount which is essentially 0.5 mole in the finalcondensation product. The temperature is then raised to 275 C. and avacuum of 0.3 mm. is applied. Heating and stirring is continued for 1hour under these conditions. After cooling, the polymer obtained has anI.V. of 0.53 and is tough and rubbery. It is dissipated in hot water tothe extent of about 20 Wt. percent to give a clear, slightly viscoussolution. After storage of the solution for three months at roomtemperature, the water is evaporated from a portion. The residualpolymer has an I.V. of 0.54. No measurable hydrolysis has occurred.

EXAMPLE 2.

The following table shows the properties of a number of polyesters madefrom sulfonate-containing difunctional monomers. All are made as inExample 1. Although it is possible to prepare polymers as in Example 1without sodium acetate or a similar buffer, preparation isadvantageously performed in the presence of such a buffer used in anamount of about 0.01% to 1% by weight of all of the components. Suchbuffers include sodium acetate, potassium acetate, calcium acetate, etc.Polymers B, L and M are included for comparative purposes only. The molepercent figures in Table I are either for the dicarboxylic acid on theone hand or the glycol (DEG, EG, etc.) on the other hand. In both casesthe mole percent adds up to 100% and the overall condensation product(100 mole percent acid plus 100 mole percent glycol) is the desiredpolymer. Of course, as in Example 1, the reaction is ordinarily carriedout with an excess of the more volatile component which is usually theglycol, e.g., in Example 1 the reaction involves 0.500 mole 100 molepercent) of dicarboxylic acid components and 0.65 mole of glycol, ofwhich the condensation product contains 0.5 mole (100 mole percent) ofsaid glycol; hence, the total overall mole percent of components is 200mole percent which could be also called mole parts or proportions, i.e.

and Flbrous Articles Sized Therewlth. 200 mole parts overall.

TABLE I Example 2.-Polyester made with snlfonate-containing monomersMole, Sulfo- Mole, Mole, Effect of Polymer Dicarboxylic acid percentnate percent Glycol percent I.V. hot. water Isophthalic 52. 5 ATcrephthalic 25 SIP l 7.5 DEG 100 0.54 Slight dissipation.

Hexahydroisophthalic. 15 Isophthalic 50 B Terephthalic 25 SIP 101,6hexaned1o1 100 0.50 No dissipation.

Hexahydroisoph ah 15 Terephthalic... 90 SIP 100 0.51 Slight dissipation.Isophthalic. 90 SIP 100 0.53 Dissipates. E Hexahydroterephthalic 90 SIP100 0.73 Do,

Isophthalic 50 F Terephthalic 2s SIP 0.60 D0 Hexahydroisophthalic. 15Isophthalic 50 G Terephthalic 25 (4) 100 0.42 D0.

Hexahydroisophthalie. 15 FT Isop 0.48 Do. I {Isophthallc 60 100 0.55 Do.

Hexahydroterephthal1c. 30 J Isonhthalic 90 100 0.42 D0. 12' Terenhthallo92 SI]? 100 0.33 D0. L Isophthalic 98 SIP 100 0.55 No dissipation. M do96 SIP 100 0.45 D0.

See footnotes at end of table.

TABLE I---Con tinued Mole, Sulfo- Mole, Mole, Efiect of PolymerDiearboxylic acid percent nate percent Glycol percent I.V. hot water Ndo 94 SIP 100 0.42 Slight dissipation. (in 92 SIP 100 0.59 Dissipates. Pdo 90 srr 0.45 Q Adlnic 90 SIP 100 0.69 D0. R Isophthalic 90 SIP 0,48slightdlssipamn- S d0 0 SI 28 0 51 Do.

80 SIP 0'32 Dissipatcs.

so SIP 0.38

Isophthalic 50 80 v Terephthalic.. 1s SIP 0.15 D

a sop t a c W "{Hexahydroisophthalio. i 100 045 X Isophtbalic 100 1000.58 D0. Y .d0 00 100 0.31 Do.

1 SIP =5-sodiosulfoisophthalie acid.

2 D E G Diethylene glycol.

3 E G=Ethylene glycol.

4 i-sodiosultophenyl 3,5-dicarboxybenzene sulfonate.

OOOR" a 5(p-sodiosulfophenoxy)isophthalic acid, NaOaSQ-OQ See notebelow.

CO R

COOR

SO3NB 7 TE G =Triethy1ene glycol.

B CHDM=1,4-cyclohexanedimethanol (70% trans/30% cis isomers; otherratios produce similar polyesters).

0 cnlonicooonm S OaNa w (CHgCHzCHzOHh S OzNa ii H3 Noon-Each R" is an Hatom or a 1-4 carbon alkyl group the polymers of this invention.

EXAMPLE 3 Use of water-dissipatable polyester as a hot-melt adhesive forpaper A lap joint between two pieces of heavy kraft paper is made byplacing between them a film cast from a Water solution of polymer ofExample 1 and then pressing with a hot iron. When this bond is broken,either in shear or peel, the paper fails rather than the adhesive. Whenthe bonded paper is boiled with water for 10 min. the bond is completelydestroyed and the polyester is dissipated.

EXAMPLE 4 Use of water-dissipatable polyester as a coating and ahot-melt adhesive for p0ly(cthylene terephthalate) film -Poly(ethyleneterephthalate) film, 10 mils thick, is

and is eliminated during the preparation of EXAMPLE 5 Use ofwater-dissipatable polyester as a packaging film A film is cast from awater solution of Polymer D of Example 2. It is clear, tough, andsomewhat rubbery. A pouch is formed from this film, filled with a soliddetergent, and heat-sealed. This package is dropped into 13 vigorouslystirred hot water. The package rapidly disintegrates releasing itscontents.

EXAMPLE 6 Modification of water-dissipatable polyester by 14 ester in100 ml. of said solvent, said polyester consisting essentially of thefollowing components:

(I) At least one difunctional glycol containing two CR H groups of whichat least 15 mole percent is a poly(ethylene glycol) having thestructural formula:

replacement of sodium 1011 f H'OCH2CH2 011 A film cast from the polymerof Example I is swelled A by soaking in water at 25 C. The water is thenreplaced n bein I g an integer of about 2 to about 20, and 22 52 :z i ii zg gggfi ?221 22 i g ig ggf z (II) At least one difunctionaldicarboxylic acid of by cold water but is still dissipatable in hotwater In a 8 Percent P similar fashion the sodium ion replaced with Ccent 18 a difunctional sulfo-mo nomer conslstmg essential- Mg++ Ni++ .1.and Fe+++ In each. case the film 1y of an aromatlc dicarboxylic acrdcontaimng a metal end n m b t ble sulfonate group attached to anaromatic nucleus. i H on SW6 mg m co Wa er u S 1 lsslpa a 15 Anespecially useful linear polyester of the aforesaid mhot Waterdefinition is the condensation product of the following The foregoingdisclosure clearly describes advantageous m onom er com ponents.embodlglepts of thls mventmn Whlch includes (1) At least onedifunctional dicarboxylic acid comwater-dissipatable polyester, havingan inherent viscosity ponent,

. at least about and .genenfflly at least abollt '3 20 (2) A hydroxycomponent which is at least one difuncrived from at least onedifunctional dicarboxylic 3.6111 at tional glycol containing two groupsa least one glycol of wh1ch at least 15 mole percent is a dmxycarboxylicacid containing one group poly(ethylene glycol) havlng the structuralformula or combination thereof (3) At least one sulfo-monomer componentwhich is included as a part of component (1), component (2), or

\ A a combination of components (1) and (2),

(4) At least one poly(ethylene glycol) component It being an integer Ofabout 2 to about and a difunchaving the following tructural formula:tional sulfo-monomer containing a metal sulfonate group attached to anaromatic nucleus. 00 H, 0

The foregoing disclosure is illustrative of a more broad A definition ofthis invention which covers a linear, waterwherein n is an integer inthe range of 2 to about 20, dissipatable polyester of polyesteramide ofcomponents component (4) being as at least about 20 mole percent of asdescribed hereinabove wherein the overall total of the sum of (i) themoles of said glycol and (ii) one half said components comprises atleast 10 mole percent of of the moles of said hydroxycarboxylic acid,the ratio of at least one or a mixture of said poly(ethylene glycols)hydroxy to carboxy groups in the total of all monomer and at least 4mole percent of at least one or a mixture of components beingsubstantially unity in the condensation said difunctional sulfomonomercomponents, said perproduct, i.e. the polyester produced. centages beingbased on the sum of the moles of all com- The following Table IIillustrates such polyesters which ponents. are prepared essentially asdescribed in Example 1 above.

These linear polyesters or polyesteramides are derived The molepercentages given for the dicarboxylic acid from monomer componentswhich can be more specificalcomponent when combined with the percentagefor the 1y identified as dicarboxylic acid, hydroxycarboxylic acid, SIPcomponent and half of the percentage for the hyaminocarboxylic acid,aminoalcohol, glycol and/or didroxycarboxylic acid component will give atotal which amine, including combinations of these components. will bemole percent of all components, and the per- In other words, one aspectof this invention provides centages given for the glycol component whensimilarly a linear, water-dissipatable polyester or polyesteramidecombined with one half of the percentage for the hyderived from at leasttwo difunctional monomer compodroxycarboxylic acid will give a totalwhich will be 50 nents which are dicarboxylic acid, hydroxycarboxylicacid mole percent. The condensation of the components rephaving one CROH group, aminocarboxylic acid, 50 resented by these two 50 mole percentsums produces the aminoalcohol having one --CR OH and one NRH desiredpolyester which could also be defined in terms group, glycol having twoCH OH group, and diamine of mole parts rather than mole percent whereinall of the components having two NRH groups, including comcomponentstaken together add up to 100 mole parts in binations thereof wherein theoverall total moles of said the condensation products, i.e. thepolyester which is procomponents comprises at least 7.5 mole percent ofat duced. It is noted that this method of measuring mole least one or amixture of poly(ethylene glycols) containpercentages and mole parts isnot the same as that used ing from 2 to 20 ethylene groups and at least4 mole perelsewhere in this specification. The important point to centof at least one or a mixture of difunctional sulfoobserve is that theratios elsewhere identified in this monomers containing at least onemetal sulfonate group specification will be essentially unity in thecondensation attached to an aromatic nucleus, said nucleus beingprespolymers being produced. ent in at least one of the aforesaidmonomer components. Table 11 illustrates polymers of this inventionwherein More especially, another aspect of this invention protheinherent viscosity is at least about 0.3, the percentage vides a linear,water-dissipatable polyester, having an inof poly(ethylene glycol) incomponent (b) is at least herent viscosityof at least about 0.1,measured in a 60/ about 20%, said n is an integer in the range from 2 to40 parts by weight solution of phenol/tetrachloroethane about 10 andeach R is an H atom, methyl, ethyl, a at 25 C. and at a concentration of0.25 gram of polypropyl isomer or a butyl isomer.

TABLE II Hydroxyearboxylic acid Sulfomonomer Diearboxylic acid (molepercent (mole percent of all ol p r n of Glycol (111019 Percent ofEffect of Polymer of all monomers) monomers) all monomers) all monomers)I.V. hot water$13131:iiiiiifiditiiitfk:::"":::::::::::Fiiiifitlffitffi?99:13:: Si?5313:: bi Ei:::::::::::::::::: 3:53 iii CC Isophathlie (27.5)4-hydroxymethy1cycl0- SIP (10) DEG (20); EG (17.5)..---.-. 0.42 Do.

hexanecarboxylic (25).

DD Sebacic G-hydroxyhexanoic (25) SIP (7.5) DEG (17.5); 1,6hexanediol1.09 Do.

' DE 2. 0.4 D

The polyesteramides according to one aspect of this invention are setforth in a more general form hereinabove. More particularly thisinvention provides such a polymer which is a polyesteramide having about20 to about 97% carbonyloxy interconnecting groups and, conversely,about 80 to about 3% carbonylamido interconnecting units in the linearmolecular structure, the latter being from said amino compounds or amixture thereof contained in said component ((1).

More specifically such polymers are those wherein said difunctionalsulfo-monomer (c) is derived from a dicarboxylic acid and constitutesabout 8 mole percent to about 50 mole percent based on the carboxylcontent, i.e., the sum of (1) the moles of component (a), (2) one halfof the moles of any hydroxycarboxylic acid and any aminocarboxylic acid,or mixture thereof contained in said component ((1), and (3) the molesof component In another more specific embodiment such polymers are thosewherein said sulfo-monomer (c) is a glycol and constitutes about 8 molepercent to about 50 mole percent based on the hydroxy and amino content,i.e., the sum of (1) the total glycol content measured in moles of (b)and (c), (2) one half of the moles of any hydroxycarboxylic acid oraminocarboxylic acid content from said component (d), and (3) moles ofany amino-alcohol or moles of any diamine content from said component((1).

In another more specific embodiment such polymers are those wherein saidsulfo-monomer (c) is a glycol and constitutes about 8 mole percent toabout 50 mole percent based on the hydroxy and amino content, i.e., thesum of ('1) th'e total glycol content measured in moles of (b) and (c),(2) one half of the moles of any hydroxycarboxylic acid oraminocarboxylic acid content from said component (d), and (3) moles ofany amino-alcohol or moles of any diamine content from said component(d).

In another more specific embodiment such polymers are those wherein saidsulfo-monomer (c) is present in more than mole percent to about 50 molepercent based on said sum of (l), (2) and (3).

The following examples provide more specific illustrations of thepolyesteramide embodiments of this invention although the processesillustrated are essentially those well known in the art as described inpatents: US. 2,901,466; US. 3,033,822; US. 3,033,826 and US. 3,033,827,the process descriptions of which are incorpo- 16 EXAMPLE 7Polyesteramide from 80 mole percent isophthalate/ZO mole percent5-sodiosulfoisophthalate esters and 40 mole percent diethylene glycol/60 mole percent hexamethylenediamine The following reactants are placedin a 100 ml. single neck flask: 15.5 g. (0.08 m.) of dimethylisophthalate, 6.0 g. (0.02 m.) of dimethyl 5-sodiosulfoisophthalate, 8.5g. (0.08 m.) of diethylene glycol, 7.0 g. (0.06 m.) of 1,6-hexanediamineand 15 ml. of water. The flask is fitted with a metal stirrer and a headhaving a nitrogen inlet tube and an outlet for downward distillation.The flask is heated in a metal bath for 7 hrs. at 90-95 C. undernitrogen. The temperature is raised to 120 C. for 1 hr. and finally to150 C. for 0.5 hr. The mixture is cooled to room temperature and 0.028g. dibutyl tin diacetate is added as a catalyst to increase molecularweight. The flask is again placed in a metal bath at 200 C. and thetemperature is raised to 270 C. The reaction mixture is heated undervacuum at 270 C. for 1.5 hrs. The final polymer has an I.V. of 0.17 andit is dissipatable in water at room temperature.

Other polyesteramide compositions as set forth in Table III are preparedby a similar procedure.

EXAMPLE 8 Polyesteramide from 60 mole percent caprolactam/40 molepercent 5-sodiosulfoisophthalate ester and 100 mole percent diethyleneglycol.

The polyesteramide is prepared as above from 21.0 g. (0.16 m.)epsilon-aminocaprolactam, 12.0 g. (0.04 m.) of dimethyl5-sodiosulfoisophthalate, 2.1 g. (0.04 m.) diethylene glycol and 2 ml.of water. The polymer has an I.V. of 0.13 and is dissipatable in hotwater (80 C.).

EXAMPLE 9 The following Table III shows properties of a number ofpolyesteramides which are made as in Examples 7 and 8. All of thepolymers of Table III are made with the designated dicarboxylic acidsand the table shows the mole percent of the acids including5-sodiosulfoisophthalic acid which is employed in an amount such thatthe total of dicarboxylic acids is 100 mole percent. The molepercentages of diethylene glycol (DEG) and diamine also add up to 100mole percent.

The diamines set forth in Table III are 1,4-cyclohexanebismethylamine inits essentially trans isomeric form (CHBMA),1,6-diamino-2,2-trimethylhexane (DATMH), hexamethylene-diamine (HMDA)and l,10-diamin0-4,7-

rated herein by reference. dioxadecane (DADOD).

TABLE III Polyesteramides with sulfonate-containing monomers Moi Mole,Dicarboxyiie Mole, percent percent Mole, Eifect of Polymer acid percentSIP DEG Diemine percent I.V. Ta, C. Tm, 0. hot water 1 Terephthalic.. 8020 CHBMA 50 0.20 127 Not detected Slight dissipation. 2..- Isophthalie..80 20 50 OHBMA. 50 0.14 120 196 (week) Dissipates. 3... do 90 10 50CHBMA 50 0.17 Not detected-- Slight dissipation. 4-.- Azelaio 80 20 50CHBMA 50 0. D0. 5.-- Isophthalic--- 20 40 CHBMA 60 0.19 6. Terephthalic80 20 60 CHBMA 40 0.15 1

.do 10 60 CHBMA 40 0.18 No dissipation.

Isophtha 90 10 60 CHBMA 40 0.16 Slight dissipation. Azelaic. 90 10 60CHBMA 40 0.37 No dissipation. 0.. 80 20 60 OHBMA 40 0.21 D0. o. 80 20 70CHBMA 30 0.26 Dissipates. Tereph 80 20 50 HMDA 50 0.18 Slightdissipation. Isophthalie 80 20 50 HMDA 50 0.15 6 Dissipates. A iaic 8020 50 HMDA 60 0.31 Do. 15 80 20 40 HMDA 60 0.17 Do. 16 90 10 60 HMDA 400.20 D0. 17 9O 10 40 HMDA 60 0.20 155 Slight dissipation.

90 10 30 HMDA 70 0.20 Not detected D0. 80 20 30 HMDA 70 0.18 dDissipates. 80 20 40 HMDA 60 0.32 Not detected No dissipation. 80 20 50HMDA 50 0.28 Slight dissipation. 90 20 00 HMDA 40 0.47 DiSSipateS. 80 2060 DATMH 50 0.15 Not detected to -10 C 122; 152; 164; 182... D0. 90 2050 DATMH 50 0.18 82 Not detected Slight dissipation. 80 20 50 DATMH 500.15 69---. 149; 158 Do. 26.. 80 20 50 DAIMH 50 0.33 6 Not detectedDissip cs. 27 Terephthalic 80 20 60 DATMH 50 0. 18 Not detected to 39 C-Do. 22 ISOphthalic. 80 20 40 DATMH 60 0.13 84 D0. 89 Azelaic 80 20 40DATMH 60 0.28 Do.

TABLE III-Continued Mole, Mole, Dicarboxylic Mole, percent percent Mole,Eflect of Polymer acid percent SIP DEG Diamine percent LV. 'Ig, C. Tm,0. hot water 30 .do- 90 10 40 DATMH 60 34 13 167 N0 dissipation.

90 50 DATMH 50 0.28 Dissipates: 80 20 50 DADOD 50 0.12 Do. 90 10 50DODAD 50 0.20 Do. 80 20 50 DADOD 50 0. 16 4; 156- Do. 90 10 50 DADOD 500.17 46 Not detected Do. 80 20 50 DADOD 50 0. 27 Not detected to -10 C-53; 75 Do. do 90 10 50 DADOD 50 0.51 Not detected to C- 69 Do. 38Isophthalic-.. 8O 40 DADOD 60 0.15 59 116 Do. 39--. -do 80 20 30 DADOD70 0.17 Do. 80 20 20 DADOD 80 0.17 D0. 80 20 20 DADOD 80 0.34 Do. 90 1020 DADOD 80 0.48 No dissipation. 90 10 30 DADOD 70 0.50 Dissipates.

The abbreviations or symbols for the diamines are given above. Tg is theglass transition temperature determined by scanning the polymers atincreasing temperatures using a Perkin-Elmer Differential ScanningCalorimeter (DSC) Model 1-B. Tm is the melting temperature measured indegrees centigrade on the same instrument. The expression Not Detectedmeans that the DSC showed no detectable endotherm which wouldcharacterize melting temperature or no detectable base line shift whichwould characterize glass transition temperature. Several values for Tmmeans that several endotherms were detected.

Polymers in Table III numbered 7, 9, 10, 20, 30 and 42 may not beillustrative of what is claimed by the present invention because thesepolymers were not readily dissipatable in water having the temperatureindicated above when no caustic was present. However, the data anddescription in this disclosure in its entirely make it readily apparentto those having ordinary skill in the art how to prepare similarpolymers which will, in general, be dissipatable in hot or coldwater orin alkaline aqueous solutions.

Additional data is given in Table IV. This data, along with the datagiven hereinabove, provides information for preparing a very extensivevariety of dissipatable polymers having a wide range of properties. Thisspecification as a whole .makes it quite clear that it is readilyfeasible to prepare water dissipatable polymers having specificproperties according to any particularly desired end use as describedhereinabove.

In Table IV, N.D. means not detected as explained above in regard toTable III.

TABLEEIV Characteristics and properties of dissipatable polyesterswherein the sulfo-monorner is SIP and the sole glycol is DEG Propertiesof pressed film Tensile properties Polymer properties Durom- Mole Yield,.Break, Percent eter Appearance Dicarboxylic acid (mole percent of sumof dicarboxylic percent To, Tm, p.s.i. p.s.i. elonhardness of pressedacid in this column and SIP) SIP LV. 0. C. X10 X10 gation at 23 C. filmIsophthalic (90) 10 0.43 25 N.D. 1.3 1.2 227 72 Hard. Terephthalic (90)10 0.39 25 171 1.0 800 272 63 Do. Isophthalic 0) 20 0.37 33 N.D. 4.9 4342 78 Do. Adipic (90) 10 0.39 N.D. 38 20 28 10 Soft; sticky.Hexahydroisophthalic (80) 20 0.34 8 N.D. 560 360 31 Flexible.

dipie (42.5); isophthalic (4 15 0.37 17 144 110 80 933 20 Soft;flexible,

Hexahydroisophthalic (42.5) isophthalic (42 5)- 15 0. 41 4 N.D. 830 56644 Flexible.

Terephthalic (42.5); isophthalie (42.5) 15 0.35 28 191 1.9 1.5 150 74Hard; brittle.

Hexahydroisophthalic (42.5); Adipic (42.5)- 15 0.38 33 N .D. 90 50 28618 Flexible. Terephthalic (42.5); adipic (42. 15 0.35 -17 147 110 50 90118 Do. Heigagggdroisophthalic (28.34); adipie (28.33); isophthalic 150.37 -13 N.D. 140 50 1369 20 Do.

Terephthalic (28.34); adipic (28.33); isophthalic (2833)..-. 15 0.34 8N.D. 140 350 828 25 D0.

Hexahydroisophthalic (90) 10 0.42 13 N.D. 80 50 108 10 Soft; sticky.Hexahydroisophthalie (8 20 0.20 -11 N .D. 400 405 30 Flexible.Teiieprhtlhalgc 3(553.34); hexahydroisophthalie (28.33); iso- 15 0.35 11N.D. 830 355 Do.

p t aie 28. 'Ierephthalie (28.34); hexahydrolsophthalic (28.33); adipie15 0.33 14 176 90 140 390 18 Do.

8.3 Terephthalie (21.25); hexahydroisophthalio (21.25); adipie 15 0.3111 N.D. 430 588 38 D0.

(21.25); isophthalic (21.25). Isophthalic (90) 10 0.26 29 N.D. 460 730343 68 Hard. Adipic (90) 10 0.25 52 N.D. 8 Soft; sticky.-

Hexahydroisophthalic (90)-- 10 0.25 20 173 11 Do.

Terephthalie (80%) 20 0. 26 22 N .D. 500 390 377 58 Hard. 22 -.do 200.20 20 N.D. 410 4 70 Do. 23 Adipic 20 0.20 46 186 35 20 30 16 Soft;sticky. 24 Terephthalio (22.5); hexahydroisophthalic (22.5); adiplc 100.43 9 134 100 759 12 Sticky.

(22.5); isophthalio (22.5). Terephthalic (42.5);hexahydroisophthalic(42.5) 15 0.36 4 N.D. 590 520 38 Flexible. Adipic (80) 20 0. 27 45 N.D.146 70 51 13 Soft; sticky:

20 0.27 14 183 176 75 286 30 Flexible.

Terephthalic (20); hexahydroisophthalic (20); adipic (20);

isophthalic (20).

*The tensile yield measurement was not considered significant.

It is readily apparent that this invention includesthe polymers asdefined when dissipated in water whether the water be (1) hot, (2) cold,(3) alkaline aqueous solutions, or any other aqueous media includingorganic or inorganic solutes, organic liquids, organic dyes, pigments,stabilizers or other additives, any of which substances may be presenttherein for the purpose of contributing to the intended end use. Whenthe expression hot water" is used, it means water at about 8090 C.unless otherwise set forth. When the only liquid present is water, thewater-dissipated polymer generally contains 0.1 to 55% by weight ofpolymer based on the sum of the polymer and water; advantageous rangesfor various end uses include 10 to 40% polymer, especially 20 to 35%polymer, etc. However, when other substances are also present, thesepercentage ranges may be considerably different.

USING AQUEOUS POLYMER BLENDS WITH OTHER SUBSTANCES Various general aswell as specific end uses for the polymers of this invention have beendescribed hereinabove. Many desirable end uses may be achieved, as foundby coworkers in our same laboratories, by altering the physicalproperties of the polymers of this invention by providing blends ofthese polymers with water and other substances, some of which have beenreferred to above in a more or less specific manner. When used forcertain particular purposes, the polymers of this invention which havebeen dissipated in water have certain properties which may diminishtheir most effective utilization. For instance, certain of the polymersof this invention have excellent adhesion on polyester fibers when usedas a sizing agent, but tend to be sticky or tacky and may thereby causedifficulty in textile processing operations. In such cases, it isdesirable to reduce the tackiness of the coating and at the same timeretain good adhesion on the fiber. In other instances, the polymers ofthis invention have excellent adhesion on substrates but are notsufficiently tacky to provide the maximum obtainable contact adhesionand in such cases it is desirable to increase the surface tackiness andstill retain the good adhesive properties on the substrate.

Therefore, the polymers of this invention may be blended with certainother substances which are compatible with the polymers of thisinvention for the intended end use, whereby the blended compositionforms transparent films or coatings having improved characteristics. Inother instances, added substances may be used which increase thehardness and reduce the tackiness of the polymers of this invention. Instill further instances, other added substances have the oppositeeffect. It is thus apparent that added substances may be employed whichprovide methods for imparting a wide range of useful supplementalcharacteristics so as to further enhance the utilization of the presentinvention to its more extensive advantage.

The results obtained by our coworkers show that in general, theseadvantageous aqueous compositions containing the polymers of the presentinvention comprise the following ingredients (A), (B) and (C):

(A) From about -96 weight percent of at least one polymer according tothe present invention, said percent being based on the sum ofingredients (A) and (B),

(B) From about 95-4 weight percent of a substance selected from thegroup generally consisting of the following substances, said percentbeing based on the sum of ingredients (A) and (B):

(l) starch (modified or natural form),

(2) carbohydrate plant gum,

(3) protein,

(4) a polymer containing amide groups,

(5) poly(vinyl alcohol),

(6) partially hydrolyzed poly(vinyl acetate),

( a a di o p ymer containing a carbo yl g up,

(8) carboxymethyl cellulose, (9) poly(alkene ether), etc.

(C) Water in an amount whereby said ingredient (A) is present in anamount of about 0.1 to about 55% based on the sum of said water andingredient (A).

The preceding weight percentages of ingredient (B) can in some instancesbe more advantageously from 10-50 weight percent or in some instances,lO-30%. According to this additional disclosure of utility, it isfurther noted that the amount of the sulfo-monomer component (c) whichis present in the polymers of this invention to facilitate enhancing thewater-dissipatable characteristic may be increased or decreaseddepending upon those other substances which may be present so as toenhance said characteristic. Moreover, the presence of other componentsin the polymers of this invention will also constitute a factoraffecting thischaracteristic as well as other characteristics, forexample, whether the polymer includes poly(ethylene glycols) containingtwo, four, six, ten, fifteen or other numbers of ethyleneoxy groups mayaffect the overall characteristics of the aqueous composition. Inaddition, the presence of component (b) in the polymer of this inventionwhich is a glycol having branched chain or alicyclic structure may alsoaffect various characteristics, such glycols being represented by2-methyl-l,4-butanediol, 2,2,4,4-tetramethyl- 1,3-cyclobutanediol,1,4-cyclohexanedimethanol, 1,2-propylene glycol, 2,3-butylene glycol,etc. The poly(ethylene glycol) may also be substituted or supplementedin some instances by glycols wherein n has a greater value than 20 suchas having a value up to 30 although when the value of n is greater than20 it must be determined whether the increased value will adverselyalfect an especially desired characteristic even though there may be anoffsetting factor due to some other additive substance such as asurfactant as illustrated by sorbitan monolaurate mixed with ethyleneoxide, or the like.

The blends of the polymers of this invention and the other substanceswhich have been mentioned above can be prepared at various temperaturesand under a wide variety of conditions depending upon thecharacteristics of the polymers of the invention which are beingemployed as well as the other substances which are being blended. Forinstance, a polymer of the invention can be dissipated in water and thiscan then be mixed with the other substance or with a solution orsuspension of the other substance or substances.

Examples of the other substances mentioned hereinabove include starch,modified starch, degraded starch, natural starch, and other forms ofstarch derived from corn starch, potato starch and includeacid-hydrolyzed starch, dextrins and the like. Carbohydrates plant gumsinclude the gum arabic, gum tragacanth, alginic acid, etc. Among themany proteins which can be employed are gelatin, casein, soybeanprotein, animal blood protein, etc. A great variety of addition typepolymers can be employed, especially those containing amine groups whichare represented by homopolymers and copolymers of acrylamides,methacrylamides, fumaramides and other amide derivatives ofa,/3-unsaturated carboxylic acids. The nitrogen atom of the amide groupmay contain one or two lower alkyl radicals as substituents. Typicalexamples are polyacrylamide, polymethacrylamide,poly(N-methylmethacrylamide) and poly(N,N-dimethylacrylamide). Otheraddition type polymers include poly (vinyl alcohol) or partiallyhydrolyzed poly(vinyl acetate) containing up to about 30 mole percent ormore of acetyl groups. Other related polymers and copolymers can beused. Further examples of addition polymers include those which containcarboxyl groups and these polymers are typically represented byhomopolymers and copolymers of acrylic acid, methacrylic acid, fumaricacid, maleic acid, itaconic acid and citraconic acid. Typical examplesare poly(acrylic acid), poly(mcthacrylic ployed are carboxymethylcellulose polymers and derivatives. These polymers may be used as thealkali metal or amine salts. Other additive substances include poly(alkylene others) as mentioned hereinbefore with particular care thatthe substances of this nature do not have a molecular Weightsutficiently high to interfere With the water-dissipatablecharacteristic of the overall liquid aqueous composition. A molecularweight of about 3000 is normally considered about maximum although insome instances higher molecular weights might be used depending upon theother substances which may be present. It is noted that thesepoly(alkylene ethers) are additives and are not considered in the senseof being one of the components of the polymers of the invention.Segmented or block type copolymer additive substances may be used whichcontain alternating segments of poly (ethylene glycol) andpoly(propylene glycol) units. This type is available commercially underthe trade name Pluronic, manufactured by Wyandotte ChemicalsCorporation.

The uses of the polymers of this invention in blends with othersubstances contain from about to 96% of the polymers of this inventionbased on the combined weight of the polymers of this invention and theother substances, excluding water.

More specific uses are illustrated by selecting a particular polymer inaccordance with this invention such as that described hereinabovederived from components (a), (b) and (c) wherein component '(a) isisophthalic acid, component (b) is diethylene glycol, and component (c)is sodium '5-sulfoisophthalate, the polymer having LV. of about 0.6.This polymer of the present invention is hereinafter referred to asPolymer X. Although Polymer X has many useful purposes some propertiescan be further enhanced, as mentioned hereinabove, where it is desiredto reduce its normal slightly tacky characteristics such as when thepolymer is used as a size for fibers which might in some cases tend toadhere to each other when wound on a beam. Moreover, such sized fibersmight in some cases tend to stick to guides, reeds and other objectsencountered during textile processing. The specific Polymer X mentionedhereinabove and the water-dissipated compositions, including Polymer X,may have one or more of their characteristics altered by blending withsubstances including those mentioned hereinabove in order to increasethe hardness and reduce the surface tack of the films and coatingsthereby obtained as follows:

(a) Four parts of Polymer X and one part of poly (vinyl alcohol) aredissolved (dissipated) in 95 parts of water. The solution is poured ontoa glass plate and the water is evaporated. The resulting film has asmooth, non-tacky surface. Pieces of the film, when pressed together, donot stick or block, whereas unmodified Polymer X films adhere stronglywhen the surfaces are contacted. The blend has excellent adhesion onpolyester, nylon and acrylic fibers. The sized fibers have essentiallyno tendency to adhere to each other when wound on a beam. There isessentially no tendency to stick on guides and reeds during processing.

(b) A blend of four parts Polymer X and one part gelatin is prepared asdescribed above. Films and coatings made from the blends have anon-tacky surface and are considerably harder than those made fromPolymer X alone. The blends are valuable as sizing agents for polyester,nylon, acrylic and cellulose ester fibers.

(c) A blend of four parts Polymer X and one part poly(acrylic acid isprepared as described above. Films cast from the water solution areclear and hard, with a non-tacky surface. The films show no tendency toad- 22 here or block when pressed together. This blend is valuable as asize for polyester, nylon, acrylic and cellulose acetate fibers.

(d) A blend of four parts Polymer X and one part sodium carboxymethylcellulose is prepared as described above. Films and coatings made fromthe blend have a non-tacky surface. Polyester fibers sized with theblend have good processing properties. The coating has excellentadhesion on the fiber and is not removed by contact with guides orreeds. The size is readily removed from the woven fabrics by standardboil-off procedures.

(e) A blend of four parts Polymer X and one partpoly(N-isopropylacrylamide) is prepared in water. Films and coatingsmade from the blend are non-tacky. Although the films are somewhatharder than Polymer X per se, they are not brittle. This blend isvaluable as a size for polyester, nylon, acrylic, glass and celluloseester fibers.

(f) A blend of four parts Polymer X and one part soluble corn starch isprepared. The composition is useful as a size on synthetic fibersbecause it has good adhesion and provides a smooth, low-frictionsurface.

All of the blends described above are readily removed from the fibers bystandard scouring procedures.

The blends are useful for producing a smooth, hard finish on paper. Thefinish imparts good printing properties.

The polymers of this invention, such as illustrated by Polymer X, may beimproved by blending with certain water-soluble polymeric substances inorder to increase the tackiness and improve the adhesive properties.

(g) A blend of four parts Polymer X and one part Carbowax 6000 isprepared in water. Carbowax 6000 is a poly(ethylene glycol) sold byUnion Carbide Chemical Co. It has the structure H(OCH CH ),,OH where nis about 150. Films and coatings made from this solution are soft andsticky. They have a high degree of surface tack and make excellentcontact adhesives. They have excellent adhesion on glass, metals,plastics, paper, wood, cellulose esters and ceramics. The solution iscoated on cellophane tape to give a layer 1 mil thick when dry. Thistape adheres to a variety of substrates when used as a contact adhesive.Similar results are obtained when a tape made from poly(ethyleneterephthalate) is used. A coating of the blend is applied on glassbottles and the water is evaporated. Paper labels are applied on thecoated bottles, using a high speed processing machine. The labels haveexcellent adhesion but can be removed by soaking for a few minutes inwater.

(h) A blend is made from four parts of Polymer X and one part ofPluronic L-64 by dissolving in water. Pluronic L- 64 is a segmentedpoly(ethylene oxidepropylene oxide) copolymer manufactured by WyandotteCo. The blend forms a tough, sticky film or coating that has excellentadhesion on metals, glass, wood, paper and plastics. It is valuable as acontact adhesive. The coatings are readily soluble in water. Thisproperty is important when it is desired to remove labels, maskingtapes, protective coatings, etc.

Blends of additional polymers of this invention such as can beidentified as Polymer Y are made as listed below, said Polymer Y beingharder and having less surface tack than said Polymer X. These blendsinclude water in a manner analogous to that described above; theabbreviation pt. means parts by weight:

(i) 50 pt. polymer Y+50 pt. soluble starch;

(j) 95 pt. polymer Y+5 pt. styrene-maleic acid copolymer, sodium salt;

(k) 70 pt. polymer Y+30 pt. casein;

(l) 70 pt. polymer Y+30 pt. gum arabic;

(m) pt. polymer Y+15 pt. polyacrylamide.

The compositions are useful as sizing agents for textile fibers and ascoating agents for paper. Films and coatings are readily removed bysoaking in water.

White, opaque coatings are obtained by incorporating 1 to 10% of apigment such as TiO clay or CaCO The polymers of this invention can beconverted into a useful contact adhesive by incorporating 10 to 30% ofCarbowax 2000, Carbowax 4000 or Pluronic L-43, which are similar tothose of g and h above. The tackiness of the polymers of this inventionare also improved by incorporating 5 to 35% of poly(ethylene oxide)derivatives having the structure where R is a hydrocarbon radicalcontaining from 6 to 20 carbon atoms and m is 10 to 60.

Other polymers of this invention including polyesters andpolyesteramides may be used in a manner similar to the use of Polymer Xand Polymer Y. Such uses include coating on tire cord as previouslymentioned above.

The foregoing discussion of utility concerning the polymers of thisinvention has been concerned to a considerable degree with blends withsubstances wherein the blends (excluding water) contain 50% or more ofthe polymers of the invention. Other uses may employ blends containing 5to 50% of the polymers of the invention whereby the relatively smallamount thereof will impart valuable adhesive properties to a widevariety of polymeric substances. The discovery of enhanced adhesion bycoworkers in our laboratories provided by such small percentages,especially to 30% of the polymers of this invention, when blended withsubstances such as starch, gelatin, natural gums and otherwater-dissipatable substances which normally have poor adhesion onhydrophobic substrates, was unexpected. Normally, small amounts such as15 to 30% of the blend polymer of the invention, along with the othersubstances, based on the total weight of the solids (excluding water),would not be expected to have a high degree of adhesion on polyesterfibers and other hydrophobic fibers, including vinyl chloride, polymericfibers and fibers derived from vinylidene chloride, etc. In fact, inmany instances percentages as little as 5% will provide satisfactory andquite unexpected results in regard to such adhesion.

The following additional illustrations of utility describe aqueouscompositions including the previously identified Polymer X; theseillustrations particularly pertain to the use of small proportions ofPolymer X for improving adhesion of starch and other water-solublesubstances as follows:

(11) Four parts of hydroxyethyl starch, one part of the Polymer X, andone part of glycerol are dissolved in 50 parts of water. The glycerol isadded as a plasticizer. The solution is applied as a thin layer ondrafted poly(ethylene terephthalate) film. After evaporation of thewater, a clear coating is formed. The coating has excellent adhesion onthe film. Hydroxyethyl starch containing the same amount of glycerol butno Polymer X has poor adhesion on the film. This blend of Polymer X,hydroxyethyl starch, and glycerol is useful as a textile size forhydrophobic fibers such as polyesters, nylon, poly(vinyl chloride), andcellulose triacetate. Blends containing only 5% Polymer X show improvedadhesion on the hydrophobic fibers.

(o) Ninety parts of thin-boiling starch and 10 parts of Polymer X aredissolved in 300 parts of water. Coatings are made from the solution onglass, polyester film, paper, 'steel, and aluminum. The coatings havegood adhesion. When 15 parts of glycerol is added, the composition isuseful as textile size for polyester, nylon, and cellulose acetatefibers.

(p) An aqueous blend of parts Polymer X and 80 parts gelatin has goodadhesion on glass, metals, and polyester film. The blend can beplasticized with glycerol, trimethylolpropane, sorbitol, or diethyleneglycol.

(q) An aqu ous blend f0 15 p ts Po ymer .X and 85 parts poly(vinylalcohol) has good adhesion on glass, polyester film, metals andceramics.

(r) The adhesion of aqueous compositions containing gum arabic andalginic acid is improved by blending with 5-25% of Polymer X. Forexample, 10 g. of gum arabic and l g. of Polymer X are dissolved in 25cc. of water and the solution is coated on glass. After evaporation ofthe water, the coating has excellent adhesion. The coating becomes tackywhen moistened and is useful for attaching labels to the glass. Gumarabic alone tends to flake off from the glass.

(s) One part of Polymer X and 9 parts of hydroxyethyl starch aredissolved in 60 parts of water. The mixture is used as a textile size.The adhesion is excellent on polyester and nylon fibers. The flexibilityof the coating is improved by using from 1 to 3 parts of glycerol ortriethylene glycol a's plasticizer.

(t) Two parts of Polymer X and 8 parts of soluble starch are dissolvedin 50 parts of water. The composition is useful as a textile size.

(n) One part of Polymer X and 2 parts of gelatin are dissolved in 100parts of water. Coatings made from the solution have good adhesion onpolyester films.

(v) One part of Polymer X and 4 parts of poly(N-isopropylacrylamide) aredissolved in 30 parts of water. Coatings made on glass and polyesterfilm have good adhesion.

USE IN BLENDS OF ELASTOMERIC STAPLE AND NORMAL STAPLE Anotheradvantageous utility of the present invention which has been discoveredby coworkers in our laboratories involves improving the preparation ofelastomeric yarns from blends of elastomeric staple and normalrelatively inelastic staple of other fibers which can be characterizedas inelastic or hard. Such blended elastomeric yarns containing fromabout 5 to about 30% by weight of elastomeric staple and to 70% byweight of inelastic staple are known to be useful in the preparation ofstretch fabrics and may be spun on conventional spinning equipment.However, our coworkers have found that the polymers of the presentinvention are especially advantageous when an aqueous compositioncontaining one or more of these water-dissipatable polymers is used as asize or coating primarily for the elastomeric staple which is normallycut from previously coated or sized continuous filaments. The inelasticstaple may or may not be sized or coated. The elastomeric staple can beprepared from fibers of well-known spandex elastomeric fibers such asthose described in U.S. 3,261,812; U.S. 2,929,804; U.S. 2,957,852; U.S.3,023,192; Brit. 1,118,731; Brit. 1,118,- 732, etc. The inelastic staplecan be prepared from Wellknown fibers of polyesters, polyamides,polyacrylates, cellulose esters, etc. as Well as natural fibers such aswool, cotton, silk, etc. U.S. Pat. 3,077,006 describes the preparationof blended elastomeric staple and inelastic staple whereby elastic yarnprepared from the blend can be obtained. Other references include U.S.3,007,227 and US. 3,325,876.

By using as sizing or coating compositions the aqueous compositions ofthe present invention which include the polymers of this invention andmay include other substances, difiiculties encountered in blending,carding, and spinning yarns are greatly reduced whereby high qualityyarn can be prepared and the yarn then washed with water so as to removethe sizing or coating composition. The washed yarn is of greatlyimproved quality. Of course, in some instances the size or coating maybe left on yarn until after it has been formed into a fabric, and thenwashed in the usual manner.

In the absence of the above-mentioned coating or sizing, the elastomericportion of the staple blend tends to become stretched and breakageoccurs in many instances; moreover, in the staple blend as theelastomeric portion of the staple relaxes, it frequently does so in sucha rapid manner that it forms tight clumps that resist untangling andthereby greatly interferes with the use of the staple blend coming fromthe carding machine inasmuch as it is not uniform and is difiicult tospin into yarn having advantageous elastomeric textile properties. Itis, therefore, unexpected that the use of aqueous sizing or coatingcompositions comprising the polymers of this invention provide means forovercoming such problems when used as explained above. Less desirablyother coatings which constitute sizing or coating materials may in someinstances also be used with generally less advantageous results or theymay be included in a blended size or coating composition. These areavailable in the trade under such trade names as Elvanol sizingcomposition, Colloid sizing composition, Seycofilm sizing composition,Stymer sizing composition, etc., such commercially available sizes beingprepared from polymers such as poly(vinyl alcohol), poly(acrylic acid),poly(vinyl acetate), the sodium salt of the copolymer of styrene andmaleic anhydride, etc. Especially advantageous sizing or coatingcompositions in accordance with this use of the present inventioncomprise water-dissipated compositions containing the polymer identifiedhereinabove as Polymer X. Of course, Polymer X is merely typical andother polymers of this invention may also be similarly employed.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationand modifications can be effected within the spirit and scope of theinvention as described hereinabove.

We claim:

1. An aqueous dissipation of a linear, water-dissipatable polymer havingcarbonyloxy linking groups in the linear molecular structure wherein upto 80% of the linking groups may be carbonylamido linking groups, thepolymer having an inherent viscosity of at least about 0.1 measured in a60/40 parts by weight solution of phenol/tetrachloroethane 25 C. and ata concentration of about 0.25 gram of polymer in 100 ml. of the solvent,the polymer containing substantially equimolar proportions of acidequivalents (100 mole percent), the polymer comprising the reactionproducts of (a), (b), (c) and (d) from the following components or esterforming or ester-amide forming derivatives thereof;

(a) at least one difunctional dicarboxylic acid;

(b) from about 4 to about 25 mole percent, based on a total of all acid,hydroxyl and amino equivalents being equal to 200 mole percent, of atleast one difunctional sulfo-monomer containing at least one metalsulfonate group attached to an aromatic nucleus wherein the functionalgroups are hydroxy, carboxyl or amino;

(c) at least one difunctional reactants selected from a glycol or amixture of a glycol and diamine having two -NRH groups, the glycolcontaining two --CH OR groups of which at least 15 mole percent based onthe total mole percent of hydroxy or hydroxy and amino equivalents, is apoly(ethylene glycol) having the structural formula:

group and one NRH or mixtures thereof, wherein each R is an H atom or analkyl group of 1 to 4 carbon atoms.

2. Aqueous dissipation of claim 1 wherein the linear, water-dissipatablepolymer is a polyester having primarily carbonyloxy linking units in thelinear molecular structure.

3. Aqueous dissipation of claim 2 wherein said difunctionalsulfo-monomer (b) is a dicarboxylic acid and constitutes about 8 molepercent to about 50 mole percent based on the sum of all acidequivalents.

4. Aqueous dissipation of claim 2 wherein said difunctionalsulfo-monomer (b) is a glycol and constitutes about 8 mole percent toabout 50 mole percent based on the sum of all the hydroxy or hydroxy andamino equivalents;

5. Aqueous dissipation of claim 3 wherein said difunctionalsulfo-monomer (b) is present as at least about 10 mole percent to about50 mole percent.

6. Aqueous dissipation of claim 4 wherein said difunctionalsulfo-monomer (b) is present as at least about 10 mole percent to about50 mole percent.

7. Aqueous dissipation of claim 2 wherein said difunctionalsulfo-monomer (b) is an aromatic dicarboxylic acid and the metalsulfonate group is attached to the aromatic nucleus thereof.

8. Aqueous dissipation of claim 7 wherein the metal of the sulfonategroup is selected from the group consisting of Na, Li, K, Mg, Ca, Cu,Ni, Fe and mixtures thereof.

9. Aqueous dissipation of claim 2 wherein said difunctionalsulfo-monomer (b) is isophthalic acid containing a metal sulfonate groupattached to the aromatic ring.

10. Aqueous dissipation of claim 9 wherein said difunctionalsulfo-monomer (b) is isophthalic acid containing a sodiosulfonate group.

11. Aqueous dissipation of claim 10 wherein said sodiosulfonate group isattached to the isophthalic acid in the 5-position.

12. Aqueous dissipation of claim 11 wherein the linear,water-dissipatable polyester comprises the reaction product of:

(a) at least mole percent isophthalic acid,

(b) about 10 mole percent 5-sodiosulfoisophthalic acid, and

(c) diethylene glycol.

13. Aqueous dissipation of claim 2 wherein the linear,water-dissipatable polyester comprises the reaction product of:

(a) about 90 mole pecent isophthalic acid (b) about 10 mole percent5-(p-sodiosulfophenoxy)- I isophthalic acid, and

(c) diethylene glycol.

14. Aqueous dissipation of claim 2 wherein the polyester comprises thereaction product of:

(a) about 90 mole percent isophthalic acid,

(b) about 10 mole percent 2-(2-sodiosulfophenyl)-2- ethylmalonic acid,and

(c) diethylene glycol.

15. Aqueous dissipation of claim 11 wherein the polyester comprises thereaction product of:

(a) about 50 mole percent isophthalic acid,

about 25 mole percent terephthalic acid, about 15 mole percenthexahydroisophthalic acid;

(b) about 10 mole percent 5-sodiosulfoisophthalic acid, and

(c) diethylene glycol.

16. Aqueous dissipation of claim 2, wherein the poly ester comprises thereaction product of;

(a) about 50 mole percent isophthalic acid,

about 25 mole percent terephthalic acid, about 15 mole percenthexahydroisophthalic acid,

(b) about 10 mole percent 4-sodiosul fophenyl-3,5-dicarboxybenzenesulfonate, and

(c) diethylene glycol.

17. Aqueous dissipation of claim 11 wherein the polyester comprises thereaction product of;

(a) about mole percent isophthalic acid (b) about 15 mole percent5-sodiosulfoisophthalic acid, and

(c) diethylene glycol.

18. Aqueous dissipation of claim 12 wherein the polyester comprises thereaction product of;

(a) about 90 mole percent isophthalic acid,

(b) about 10 mole percent 5-sodiosulfoisophthalic acid, and

(c) diethylene glycol.

19. Aqueous dissipation of claim 11 wherein component (a) is a mixtureof terephthalic and adipic acid, component (b) is5-sodiosulfoisophthalic acid which is about 10 mole percent based uponthe sum of the acid equivalents and component (c) is diethylene glycol.

20. Aqueous dissipation of claim 11 wherein component (a) is at least 80mole percent of adipic acid, component (b) is about 10 mole percent5-sodiosulfoisophthalic acid and component (c) is diethylene glycol.

21. Aqueous dissipation of claim 11 wherein component (a) is isophthalicacid, component (b) is 5-sodiosulfoisophthalic acid, and component isdiethylene glycol, there being none of component (d).

22. Aqueous dissipation of claim 11 wherein component (a) is isophthalicacid, terephthalic acid, or mixtures thereof, component (b) is-sodiosulfoisophthalic acid, and component (b) is diethylene glycol.

23. An aqueous dissipation of a linear, water dissipatable polyesterhaving an inherent viscosity of at least about 0.1, measured in a 60/40parts by weight solution of phenol/tetrachloroethane at 25 C. and at aconcentration of 0.25 gram of polyester in 100 ml. of the solvent, thepolyester comprising the reaction products of following components orester forming derivatives thereof;

(1) at least one difunctional glycol containing two aliphatic hydroxygroups of which at least 15 mole percent is a poly(ethylene glycol)having the structural formula:

H \OCHz 0112/ n being an integer of about 2 to about 20; and (II) atleast two difunctional dicarboxylic acids of which (from about 8 molepercent to about 50 mole percent is a difunctional sulfomonomercomponent containing at least one metal sulfonate group attached to anaromatic nucleus.

24. Aqueous dissipation of claim 11 wherein component (a) isterephthalic acid, component (b) is 5- sodiosulfoisophthalic acid,component (c) is diethylene glycol, and component (d) is6-hydroxyhexanoic acid.

25. Aqueous dissipation of claim 1 wherein the linear,water-dissipatable polymer is a polyesteramide having from about 3% toabout 80% carbonylamido linking units in the linear molecular structure.

26. Aqueous dissipation of claim 25, wherein the difunctionalsulfo-monomer (b) is a dicarboxylic acid and constitutes about 8 molpercent to about 50 mole percent based on the sum of all acidequivalents.

27. Aqueous dissipation of claim 25 wherein said sulfomonomer (b) is aglycol and constitutes about 8 mole percent to about 50 mole percentbased on the sum of all the hydroxy and amino equivalents.

28. Aqueous dissipation of claim 26 wherein said sulfo-monomer (b)constitutes from about 10 mole percent to about 50 mole percent based onthe sum of all acid equivalents.

29. Aqueous dissipation of claim 26 wherein said difunctionalsulfo-monomer is an aromatic dicarboxylic acid and the metal sulfonategroup is attached to the aromatic nucleus thereof.

30. Aqueous dissipation of claim 29 wherein the metal of the sulfonategroup is selected from the group consisting of Na, Li, K, Mg, Ca, Cu,Ni, Fe and mixtures thereof.

31. Aqueous dissipation of claim 26 wherein said difunctionalsulfo-monomer is isophthalic acid containing a metal sulfonate groupattached to the aromatic nucleus.

32. Aqueous dissipation of claim 31 wherein said difunctionalsulfo-monomer is isophthalic acid containing a sodiosulfonate group.

33. Aqueous dissipation of claim 32 wherein said sodiosulfonate group isattached to the isophthalic acid in the 5-position.

34. Aqueous dissipation of claim 1 wherein the polymer has an inherentviscosity of at least about 0.3, the percentage of poly(ethylene glycol)in component (c) is at least about 20%, n is an integer in the rangefrom 2 to about 10 and each R is an H atom, methyl, ethyl, a propylisomer or a butyl isomer.

35. The aqueous dissipation of claim 1 containing about 0.1 to about 50%by weight of polymer based on the weight of the polymer and the wateradded together.

36. Aqueous dissipation of claim 35 wherein the percentage range isabout 20 to 35%.

37. The aqueous dissipation of claim 3 containing about 0.1 to about 50%by weight of polymer based on the weight of the polymer and the wateradded together.

38. The aqueous dissipation of claim 12 containing about 0.1 to about50% by weight of polymer based on the weight of the polymer and thewater added together.

39. The aqueous dissipation of claim 18 containing about 0.1 to about50% by weight of polymer based on the weight of the polymer and thewater added together.

40. The aqueous dissipation of claim 23 containing about 0.1 to about50% by weight of polymer based on the weight of the polymer and thewater added together.

References Cited UNITED STATES PATENTS 3,557,039 1/ 1971 McIntyre et al260292 3,092,597 6/ 1963 Leech et a1. 260--29.2 3,222,299 12/1965MacDowell 2602.3 3,310,512 3/1967 Curtice 26029.4 3,442,842 5/ 1969Bonin 26029.2

FOREIGN PATENTS 12,149 8/1962 Japan 260 S OTHER REFERENCES Coney, Def.Pub. of Ser. No. 30,249, filed Apr. 20, 1970, published in 0.6. on Mar.9, 1971, Defensive Publication No. T884,004, 26029.2.

WILLIAM H. SHORT, Primary Examiner L. L. LEE, Assistant Examiner US. Cl.X.R.

117-1388 F, R; 26075, 16, 29.2 EP, 29.2 N, 40 R, 47 OZ, 75 S, 873

Pg ggo UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo.3,734, 74 Dated Mav 22. 1973 Inventor(s) Charles J. Kibler. Gerald R.Laooin It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Column 4, line 45, delete 'l,3cyclo" and insert -l,3-eyclohexanebismethylamine-.

Column 4, lines 60-65, delete the formula and insert Column 6, line l,-(G) before 'sodiosulfo-l-naphthyl-3,5 dicarbomethoxy" insert 6-- Column6, line 16, (I) before "SOdiOSlilfOPhIlYl'vg,S-diCElIbDPIOPDXYbEIIZGHE-sulfonate" insert 4- Column 6, line 22, (J) before"sodiosulfophenyl-B,S-dicarbobutoxybenzenesulfonate", insert 4- Column13, line 32, after "polyester' delete "of and insert -or--.

Column 13, line 52, delete, "CH 0H" and insert -CR 0H Table II, PolymerDD under "Dicerboxylic acid (mole percent of all monomers)" after"Sebacic" insert --(30)-.

Column 15, delete lines 30 through 39.

Columns 15 and-16",Tab1e III under "rams", ciit isi: its numbers (22and-'89) and insert -28-- and -29--.

Columns 17 end 18', Table III, Polymer No. 33, under the column Diamine,delete "DODAD" and insert --DADOD'---.

TE C I026] .r(\-/16u9a)u U'JNLlDU Dlfllhfi tA'l'lJll'l' UillUlfiCERTIFICATE OF C'RECTIUN Patent N 3,734,874 I D ed Mav 22. 1973Inven[or(s) Charles J. Kibler, Gerald R. Laooin It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 23,- line 75", ,delete "f0" and insert ---of---.

Column 25, Claim 1, line tl, after "(100 mole percent)" insert -tohydroxy and amino equivalents (100 mole percent)--.

Column 25, Claim l,' line 55, delete 'CH -0R" and insert -CR -OH.

Column 25, Claim 1, line 66, delete "-NHR" and insert NRH Column 26,Claim 13, line 43, delete "pecent" and insert --p'ercent-.

Signed and sealed this 20th day of November 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. RENE D, TEG'IMEYER Attesting Officer ActingCommissioner of Patents L j J rec 10261

